[go: up one dir, main page]

WO2018116731A1 - Verre - Google Patents

Verre Download PDF

Info

Publication number
WO2018116731A1
WO2018116731A1 PCT/JP2017/041889 JP2017041889W WO2018116731A1 WO 2018116731 A1 WO2018116731 A1 WO 2018116731A1 JP 2017041889 W JP2017041889 W JP 2017041889W WO 2018116731 A1 WO2018116731 A1 WO 2018116731A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
less
content
strain point
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/041889
Other languages
English (en)
Japanese (ja)
Inventor
敦己 斉藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017041660A external-priority patent/JP6983377B2/ja
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to US16/469,340 priority Critical patent/US11572304B2/en
Priority to CN201780078378.5A priority patent/CN110088053A/zh
Publication of WO2018116731A1 publication Critical patent/WO2018116731A1/fr
Anticipated expiration legal-status Critical
Priority to US18/091,530 priority patent/US20230146789A1/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C03B17/064—Forming glass sheets by the overflow downdraw fusion process; Isopipes therefor
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/841—Self-supporting sealing arrangements
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates

Definitions

  • the present invention relates to glass, and more particularly to glass suitable for a substrate of an organic EL display.
  • Organic EL displays are thin and excellent in moving picture display and have low power consumption. Therefore, they are used for applications such as mobile phone displays.
  • Glass plates are widely used as substrates for organic EL displays.
  • the glass plate for this application is mainly required to have the following characteristics. (1) In order to prevent a situation where alkali ions are diffused in the semiconductor material formed in the heat treatment step, the content of the alkali metal oxide is small. (2) In order to reduce the cost of the glass plate, it is excellent in productivity, particularly excellent in devitrification resistance and meltability, (3) In the manufacturing process of p-Si.TFT, in order to reduce thermal shrinkage, the strain point is high. (4) The specific Young's modulus is high in order to reduce the self-weight deflection in the transport process.
  • Patent Document 1 discloses a glass plate having a high strain point. However, if the strain point is high, the productivity tends to decrease.
  • the present invention has been made in view of the above circumstances, and its technical problems are excellent productivity (particularly devitrification resistance), a high specific Young's modulus, and heat in the manufacturing process of p-Si TFT.
  • the idea is to create a glass with low shrinkage.
  • the inventor has found that the above technical problem can be solved by strictly regulating the glass composition of low alkali glass or non-alkali glass, and proposes as the present invention. is there. That is, the glass of the present invention has a glass composition of SiO 2 55-70%, Al 2 O 3 15-25%, B 2 O 3 0-5%, Li 2 O + Na 2 O + K 2 O 0- It contains 0.5%, MgO 3 to 10%, SrO 7 to 20%, BaO 0 to 5%, and has a strain point higher than 720 ° C.
  • “Li 2 O + Na 2 O + K 2 O” refers to the total amount of Li 2 O, Na 2 O and K 2 O.
  • strain point refers to a value measured based on the method of ASTM C336.
  • the glass of the present invention has a glass composition in terms of mass% of SiO 2 55 to 70%, Al 2 O 3 15 to 25%, B 2 O 3 0 to less than 3%, Li 2 O + Na 2 O + K 2. O 0 to less than 0.1%, MgO 3 to 10%, CaO 0.1 to 4%, SrO 8 to 20%, BaO 0.1 to 4% are preferably contained.
  • the glass of the present invention preferably has a CaO / MgO ratio of 0.7 or less in terms of mass%. If it does in this way, Young's modulus and devitrification resistance can be improved simultaneously.
  • the glass of the present invention preferably has a CaO / SrO ratio of 0.4 or less in terms of mass%.
  • the glass of the present invention preferably further contains 0.001 to 1% by mass of SnO 2 .
  • the glass of the present invention preferably has a specific Young's modulus, that is, a value obtained by dividing Young's modulus by density, greater than 29.5 GPa / g ⁇ cm ⁇ 3 .
  • the glass of the present invention preferably has a liquidus temperature lower than 1320 ° C.
  • the “liquid phase temperature” is obtained by passing the standard sieve 30 mesh (500 ⁇ m) and putting the glass powder remaining on the 50 mesh (300 ⁇ m) in a platinum boat, and holding it in a temperature gradient furnace for 24 hours. It can be calculated by measuring the temperature at which precipitation occurs.
  • the glass of the present invention preferably has a temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s of 1660 ° C. or lower.
  • the “temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s” can be measured by a platinum ball pulling method.
  • the glass of the present invention preferably has a viscosity at a liquidus temperature of 10 4.0 dPa ⁇ s or more.
  • the “viscosity at the liquidus temperature” can be measured by a platinum ball pulling method.
  • the glass of the present invention has a flat plate shape and has an overflow merging surface at the center in the thickness direction. That is, it is preferably formed by an overflow downdraw method.
  • the glass of the present invention is preferably used for an organic EL device, particularly an organic EL display.
  • the glass of the present invention has a glass composition of SiO 2 55-70%, Al 2 O 3 15-25%, B 2 O 3 0-5%, Li 2 O + Na 2 O + K 2 O 0-0. 5%, MgO 3-10%, SrO 7-20%, BaO 0-5%.
  • the reason for limiting the content of each component as described above will be described below.
  • % display represents mass%.
  • SiO 2 is a component that forms a glass skeleton and increases the strain point.
  • the content of SiO 2 is 55 to 70%, preferably 58 to 65%, especially 59 to 63%.
  • the strain point and acid resistance are likely to be lowered, and the density is likely to be increased.
  • the content of SiO 2 is large, the high temperature viscosity becomes high and the meltability tends to be lowered, and the balance of the glass components is lost, and devitrification crystals such as cristobalite are precipitated, and the liquidus temperature Tends to be high. Furthermore, the etching rate by HF tends to decrease.
  • Al 2 O 3 is a component that increases the strain point and further increases the specific Young's modulus.
  • the content of Al 2 O 3 is 15 to 25%, preferably 17 to 23%, particularly 18 to 22%. When the content of Al 2 O 3 is less, the strain point and specific Young's modulus tends to decrease. On the other hand, when the content of Al 2 O 3 is large, mullite and feldspar-based devitrified crystals are precipitated, and the liquidus temperature tends to be high.
  • the mol% ratio SiO 2 / Al 2 O 3 is an important component ratio in order to achieve both a high strain point and high devitrification resistance. Both components have the effect of increasing the strain point as described above, but when the amount of SiO 2 is relatively large, devitrified crystals such as cristobalite are likely to precipitate. On the other hand, when the amount of Al 2 O 3 is relatively large, alkaline earth aluminosilicate devitrified crystals such as mullite and anorthite are likely to precipitate. Therefore, the molar ratio SiO 2 / Al 2 O 3 is preferably 4.5 to 8, 4.5 to 7, 4.8 to 6.5, particularly 4.9 to 6.
  • B 2 O 3 is a component that enhances meltability and devitrification resistance.
  • the content of B 2 O 3 is preferably 0 to 5%, 0 to less than 3%, 0.1 to 3%, particularly preferably 0.08 to 2%.
  • BHF resistance buffered hydrofluoric acid resistance
  • the content of B 2 O 3 is preferably 0 to less than 0.1%.
  • Li 2 O, Na 2 O, and K 2 O are components that are mixed in a very small amount from impurities in the raw material, and are components that increase the meltability and decrease the electrical resistivity of the molten glass, but Li 2 O, Na When 2 O and K 2 O are contained in a large amount, there is a possibility that contamination of the semiconductor material is caused by diffusion of alkali ions. Therefore, the content of Li 2 O + Na 2 O + K 2 O is 0 to 0.5%, preferably 0.01 to 0.3%, 0.02 to 0.2%, particularly 0.03 to 0.1. %. The content of Na 2 O is preferably 0 to 0.3%, 0.01 to 0.3%, 0.02 to 0.2%, particularly 0.03 to less than 0.1%.
  • MgO is a component that increases meltability and Young's modulus.
  • the content of MgO is 3 to 10%, preferably 4 to 6.5%, 4 to 6%, particularly 4 to 5%.
  • the content of MgO is small, it is difficult to ensure rigidity and the meltability is easily lowered.
  • the content of MgO is large, Mg-based or Al-based devitrified crystals are likely to precipitate, and the strain point may be significantly lowered.
  • SrO is a component that suppresses phase separation and increases devitrification resistance. Furthermore, it is a component that increases the meltability by lowering the high temperature viscosity without lowering the strain point.
  • the SrO content is 7 to 20%, preferably 8 to 15%, in particular 8 to 13%.
  • the content of SrO is small, it is difficult to receive the above effect.
  • the content of SrO is large, the balance of the glass components is lost, and devitrification crystals of strontium feldspar are likely to be precipitated, and devitrification resistance is liable to be lowered.
  • BaO is a component having a high effect of suppressing precipitation of mullite-based devitrified crystals among alkaline earth metal oxides.
  • the content of BaO is preferably 0 to 5%, 0.1 to 4%, 0.1 to 3%, especially 0.1 to 2%.
  • a mullite devitrification crystal will precipitate easily.
  • the devitrification crystal crystallization containing Mg and Al will precipitate easily, while high temperature viscosity will become high too much and a meltability will fall easily.
  • CaO is a component that lowers the high-temperature viscosity without increasing the strain point, increases the meltability, and increases the rigidity.
  • the CaO content is preferably 0 to 4%, 0.1 to 4%, 0.1 to 3%, particularly 0.1 to 2%.
  • the mass% ratio CaO / MgO is preferably 1.0 or less, 0.7 or less, 0.5 or less, particularly 0.4 or less.
  • Young's modulus and devitrification resistance are liable to decrease.
  • the mass% ratio CaO / SrO is preferably 1.0 or less, 0.5 or less, 0.4 or less, particularly 0.3 or less.
  • Young's modulus and devitrification resistance are liable to decrease.
  • ZnO is a component that enhances the meltability.
  • the content of ZnO is preferably 0 to 5%, 0 to 3%, 0 to 0.5%, particularly 0 to 0.2%.
  • P 2 O 5 is a component that increases the strain point.
  • the content of P 2 O 5 is preferably 0 to 1.5%, 0 to 1.2%, particularly 0 to less than 0.1%.
  • TiO 2 is a component that lowers the viscosity at high temperature and increases the meltability, and is a component that suppresses the resistance to solarization. However, if TiO 2 is contained in a large amount, the glass is colored and the transmittance decreases. It becomes easy. Therefore, the content of TiO 2 is preferably 0 to 5%, 0 to 3%, 0 to 1%, particularly 0 to 0.02%.
  • ZrO 2 , Y 2 O 3 , Nb 2 O 5 , and La 2 O 3 have a function of increasing the strain point, Young's modulus, and the like. However, when the content of these components is large, the density tends to increase. Therefore, the contents of ZrO 2 , Y 2 O 3 , Nb 2 O 5 and La 2 O 3 are 0 to 5%, 0 to 3%, 0 to 1%, 0 to less than 0.1%, particularly 0 It is preferably less than 0.05%.
  • Fe 2 O 3 is a component that is inevitably mixed in from the glass raw material, and is a component that is difficult to remove completely from the glass composition.
  • the content of Fe 2 O 3 is preferably 0.001 to 0.1%, 0.005 to 0.05%, particularly 0.008 to 0.015%.
  • the content of Fe 2 O 3 is small, the use of high purity raw material is essential, the raw material cost is soaring.
  • the content of Fe 2 O 3 is large, the transmittance of the glass plate is liable to lower.
  • Fe 2 O 3 in order to reduce the electrical resistivity of the molten glass in order to perform electric melting, it is preferable to introduce Fe 2 O 3 positively, in which case the content of Fe 2 O 3 is 0 0.005 to 0.03% by mass, 0.008 to 0.025% by mass, and particularly 0.01 to 0.02% by mass are preferable.
  • SnO 2 is a component that has a good clarification action in a high temperature range, a component that increases the strain point, and a component that decreases high temperature viscosity.
  • the content of SnO 2 is preferably 0 to 1%, 0.001 to 1%, 0.01 to 0.5%, particularly 0.05 to 0.3%.
  • the devitrification crystal SnO 2 is likely to precipitate. Incidentally, when the content of SnO 2 is small, it becomes difficult to enjoy the above-mentioned effects.
  • metal powder such as F 2 , Cl 2 , SO 3 , C, Al, Si or the like can be added up to 5% as a fining agent. Further, it can be added as a refining agent, also CeO 2, etc. up to 1%.
  • the glass of the present invention does not completely eliminate the introduction of these components, but these components are used as much as possible from an environmental point of view. Preferably not. Furthermore, when a large amount of As 2 O 3 is contained in the glass, the solarization resistance tends to be lowered. Therefore, the content is preferably 0.1% or less, and it is desirable that the glass does not contain substantially.
  • “substantially does not contain As 2 O 3 ” refers to the case where the content of As 2 O 3 in the glass composition is less than 0.05%.
  • the content of Sb 2 O 3 is preferably 0.2% or less, particularly preferably 0.1% or less, and it is desirable that the Sb 2 O 3 content is not substantially contained.
  • “substantially does not contain Sb 2 O 3 ” refers to a case where the content of Sb 2 O 3 in the glass composition is less than 0.05%.
  • Cl has an effect of promoting the melting of the low alkali glass. If Cl is added, the melting temperature can be lowered and the action of the fining agent can be promoted. It also has the effect of reducing the ⁇ -OH value of the molten glass. However, if the Cl content is too large, the strain point tends to decrease. Therefore, the Cl content is preferably 0.5% or less, particularly 0.001 to 0.2%.
  • a raw material for introducing Cl a raw material such as an alkaline earth metal oxide chloride such as strontium chloride or aluminum chloride can be used as a raw material for introducing Cl.
  • the glass of the present invention preferably has the following glass characteristics.
  • the strain point is higher than 720 ° C, preferably 730 ° C or higher, 740 ° C or higher, particularly 750 ° C or higher. If the strain point is low, the glass plate is likely to be thermally contracted in the manufacturing process of the p-Si • TFT.
  • the average coefficient of thermal expansion in the temperature range of 30 to 380 ° C. is preferably 33 ⁇ 10 ⁇ 7 to 44 ⁇ 10 ⁇ 7 / ° C., in particular 35 ⁇ 10 ⁇ 7 to 41 ⁇ 10 ⁇ 7 / ° C. If the average thermal expansion coefficient in the temperature range of 30 to 380 ° C. is outside the above range, it does not match the thermal expansion coefficient of the peripheral member, and the peripheral member is likely to be peeled off or the glass plate is warped.
  • “average thermal expansion coefficient in the temperature range of 30 to 380 ° C.” refers to a value measured with a dilatometer.
  • the etching rate by HF is preferably 0.8 ⁇ m / min or more, 0.9 ⁇ m / min or more, particularly 1 ⁇ m / min or more.
  • the “HF etching rate” is based on the etching depth when a part of the mirror-polished glass surface is masked with a polyimide tape and then etched with a 5 mass% HF aqueous solution at 20 ° C. for 30 minutes. Refers to the calculated value.
  • the liquidus temperature is preferably less than 1320 ° C., 1310 ° C. or less, particularly 1300 ° C. or less.
  • the liquidus temperature is high, devitrification crystals are generated at the time of forming by the overflow downdraw method or the like, and the productivity of the glass plate tends to be lowered.
  • the viscosity at the liquidus temperature is preferably 10 4.0 dPa ⁇ s or more, 10 4.2 dPa ⁇ s or more, 10 4.4 dPa ⁇ s or more, particularly 10 4.5 dPa ⁇ s or more.
  • the viscosity at the liquidus temperature is low, devitrification crystals are generated at the time of forming by the overflow down draw method or the like, and the productivity of the glass plate is likely to be lowered.
  • the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s is preferably 1660 ° C. or lower, 1640 ° C. or lower, 1630 ° C. or lower, particularly 1620 ° C. or lower.
  • the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s increases, glass melting becomes difficult and the production cost of the glass plate increases.
  • Specific modulus is preferably 29.5GPa / g ⁇ cm -3 greater, 30GPa / g ⁇ cm -3 or more, 30.5GPa / g ⁇ cm -3 or more, particularly 31GPa / g ⁇ cm -3 or more.
  • specific Young's modulus is high, the glass plate is easily bent by its own weight.
  • the strain point can be increased by lowering the ⁇ -OH value.
  • the ⁇ -OH value is preferably 0.30 / mm or less, 0.25 / mm or less, 0.20 / mm or less, particularly 0.15 / mm or less. If the ⁇ -OH value is too large, the strain point tends to decrease. If the ⁇ -OH value is too small, the meltability tends to be lowered. Therefore, the ⁇ -OH value is preferably 0.01 / mm or more, particularly 0.05 / mm or more.
  • the following methods may be mentioned.
  • ⁇ -OH value refers to a value obtained by measuring the transmittance of glass using FT-IR and using the following equation.
  • ⁇ -OH value (1 / X) log (T 1 / T 2 )
  • X Glass wall thickness (mm)
  • T 1 Transmittance (%) at a reference wavelength of 3846 cm ⁇ 1
  • T 2 Minimum transmittance (%) in the vicinity of a hydroxyl group absorption wavelength of 3600 cm ⁇ 1
  • the glass of the present invention has a flat plate shape and preferably has an overflow merging surface at the center in the thickness direction. That is, it is preferably formed by an overflow downdraw method.
  • the overflow down draw method is a method in which molten glass overflows from both sides of a wedge-shaped refractory, and the molten glass overflows and merges at the lower end of the wedge shape, and is stretched downward to form a flat plate shape.
  • the surface to be the surface of the glass plate is not in contact with the refractory, and is formed in a free surface state. For this reason, it is possible to produce an unpolished glass plate with good surface quality at low cost, and it is easy to increase the area and thickness.
  • a glass plate by, for example, a slot downdraw method, a redraw method, a float method, or a rollout method.
  • the thickness in the case of a flat plate
  • the thickness is not particularly limited, but is preferably 1.0 mm or less, 0.7 mm or less, 0.5 mm or less, particularly 0.4 mm or less.
  • the wall thickness can be adjusted by the flow rate and the drawing speed during glass production.
  • the glass of the present invention As a method for producing the glass of the present invention on an industrial scale, as a glass composition, SiO 2 55 to 70%, Al 2 O 3 15 to 25%, B 2 O 3 0 to 5%, Li 2 A method for producing a glass plate containing O + Na 2 O + K 2 O 0 to 0.5%, MgO 3 to 10%, SrO 7 to 20%, BaO 0 to 5% and having a strain point higher than 720 ° C.
  • the obtained glass batch is supplied to a melting furnace and is heated by energization with a heating electrode to obtain a molten glass, and the obtained molten glass is made to have a plate thickness of 0.1 to 0.7 mm by an overflow down draw method. It is preferable to have the shaping
  • the manufacturing process of a glass plate generally includes a melting process, a fining process, a supplying process, a stirring process, and a forming process.
  • the melting step is a step of obtaining a molten glass by melting a glass batch prepared by mixing glass raw materials.
  • the clarification step is a step of clarifying the molten glass obtained in the melting step by the action of a clarifier or the like.
  • a supply process is a process of transferring a molten glass between each process.
  • the stirring step is a step of stirring and homogenizing the molten glass.
  • the forming step is a step of forming molten glass into flat glass. If necessary, a step other than the above, for example, a state adjusting step for adjusting the molten glass to a state suitable for molding may be introduced after the stirring step.
  • the ⁇ -OH value is 0.40 / mm or less, 0.30 / mm or less, 0.20 / mm or less, particularly 0.15 / mm or less. It becomes easy to regulate. Furthermore, when conducting heating with a heating electrode, the amount of energy per mass for obtaining molten glass is reduced and the amount of molten volatiles is reduced, so that the environmental load can be reduced.
  • the electric heating by the heating electrode is performed by applying an AC voltage to the heating electrode provided at the bottom or side of the melting kiln so as to contact the molten glass in the melting kiln.
  • the material used for the heating electrode is preferably one having heat resistance and corrosion resistance against molten glass.
  • tin oxide, molybdenum, platinum, rhodium, etc. can be used, and molybdenum is particularly preferable.
  • the glass of the present invention contains only an alkali metal oxide in an amount corresponding to impurities, the electrical resistivity is higher than that of a high alkali content glass. Therefore, when applying current heating by the heating electrode to the low alkali glass, current flows not only in the molten glass but also in the refractory constituting the melting kiln, and the refractory constituting the melting kiln may be damaged early. is there.
  • a zirconia refractory having a high electrical resistivity, particularly a zirconia electroformed brick, as a refractory in the furnace, and a component that lowers the electrical resistivity in molten glass (glass composition) It is preferable to introduce a small amount of Li 2 O, Na 2 O, K 2 O, Fe 2 O 3 and the like, and it is particularly preferable to introduce a small amount of Li 2 O, Na 2 O and K 2 O.
  • the content of Fe 2 O 3 is preferably 0.005 to 0.03% by mass, 0.008 to 0.025% by mass, and particularly preferably 0.01 to 0.02% by mass.
  • the content of ZrO 2 in the zirconia refractory is preferably 85% by mass or more, particularly 90% by mass or more.
  • Table 1 shows examples of the present invention (sample Nos. 1 to 19).
  • “NA” means not measured.
  • the content of Fe 2 O 3 in each sample is not clearly shown, but each sample contains 0.001 to 0.008 mass% of Fe 2 O 3 as an impurity in the glass composition. Yes.
  • the ⁇ -OH value of each sample is not clearly shown, but the ⁇ -OH value of each sample was 0.05 to 0.15 / mm.
  • a glass batch in which glass raw materials were prepared so as to have the glass composition shown in the table was placed in a platinum crucible and melted at 1600 to 1650 ° C. for 24 hours.
  • the mixture was stirred and homogenized using a platinum stirrer.
  • the molten glass was poured out onto a carbon plate, formed into a plate shape, and then gradually cooled at a temperature near the annealing point for 30 minutes.
  • the average coefficient of thermal expansion ⁇ in the temperature range of 30 to 380 ° C. is a value measured with a dilatometer.
  • the density is a value measured by the well-known Archimedes method.
  • the etching rate of HF is a value calculated from the etching depth when a part of the mirror-polished glass surface is masked with a polyimide tape and then etched with a 10 mass% HF aqueous solution at 20 ° C. for 30 minutes. .
  • strain point Ps, annealing point Ta, and softening point Ts are values measured based on the methods of ASTM C336 and C338.
  • the temperatures at high temperature viscosities of 10 4.5 dPa ⁇ s, 10 4.0 dPa ⁇ s, 10 3.0 dPa ⁇ s, and 10 2.5 dPa ⁇ s are values measured by the platinum ball pulling method.
  • the liquid phase temperature TL passes through a standard sieve 30 mesh (a sieve opening of 500 ⁇ m), puts the glass powder remaining in 50 mesh (a sieve opening of 300 ⁇ m) in a platinum boat, and holds it in a temperature gradient furnace for 24 hours. This is a value obtained by measuring the temperature at which crystals (initial phase) precipitate.
  • the liquidus viscosity log 10 ⁇ TL is a value obtained by measuring the viscosity of the glass at the liquidus temperature TL by a platinum ball pulling method.
  • the Young's modulus is a value measured using a well-known resonance method. Specific Young's modulus is a value obtained by dividing Young's modulus by density.
  • sample No. 1 to 19 have a low alkali metal oxide content, a strain point of 743 ° C. or higher, a temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s of 1629 ° C. or lower, a liquidus temperature of 1324 ° C. or lower, and a liquidus temperature of The viscosity was 10 4.13 dPa ⁇ s or more, and the specific Young's modulus was 31.7 GPa / g ⁇ cm ⁇ 3 or more. Therefore, sample no. Nos. 1 to 19 are considered to be suitably usable as substrates for organic EL displays.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

En tant que composition de verre, ce verre exempt d'alcali est caractérisé en ce qu'il contient, en % en masse, de 55 à 70 % de SiO2 <sb />, de 15 à 25 % d'Al2O3, de 0 à 5 % de B2O3, de 3 à 10 % de MgO, de 7 à 20 % de SrO et de 0 à 5 % de BaO, ne contient sensiblement aucun oxyde de métal alcalin, et présente une température inférieure de recuit supérieure à 720 °C.
PCT/JP2017/041889 2016-12-19 2017-11-21 Verre Ceased WO2018116731A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/469,340 US11572304B2 (en) 2016-12-19 2017-11-21 Glass
CN201780078378.5A CN110088053A (zh) 2016-12-19 2017-11-21 玻璃
US18/091,530 US20230146789A1 (en) 2016-12-19 2022-12-30 Glass

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-245057 2016-12-19
JP2016245057 2016-12-19
JP2017-041660 2017-03-06
JP2017041660A JP6983377B2 (ja) 2016-12-19 2017-03-06 ガラス

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US16/469,340 A-371-Of-International US11572304B2 (en) 2016-12-19 2017-11-21 Glass
US18/091,530 Continuation US20230146789A1 (en) 2016-12-19 2022-12-30 Glass

Publications (1)

Publication Number Publication Date
WO2018116731A1 true WO2018116731A1 (fr) 2018-06-28

Family

ID=62626242

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/041889 Ceased WO2018116731A1 (fr) 2016-12-19 2017-11-21 Verre

Country Status (2)

Country Link
US (1) US20230146789A1 (fr)
WO (1) WO2018116731A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112805255A (zh) * 2018-10-05 2021-05-14 日本电气硝子株式会社 无碱玻璃板
CN112823143A (zh) * 2018-10-15 2021-05-18 日本电气硝子株式会社 无碱玻璃板
JPWO2021261446A1 (fr) * 2020-06-25 2021-12-30
CN114080369A (zh) * 2019-08-14 2022-02-22 日本电气硝子株式会社 玻璃基板
WO2024142807A1 (fr) * 2022-12-26 2024-07-04 日本電気硝子株式会社 Substrat de verre

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1045422A (ja) * 1996-07-29 1998-02-17 Asahi Glass Co Ltd 無アルカリガラスおよびフラットディスプレイパネル
WO2011001920A1 (fr) * 2009-07-02 2011-01-06 旭硝子株式会社 Verre exempt d'alcali et son procédé de production

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5489558A (en) * 1994-03-14 1996-02-06 Corning Incorporated Glasses for flat panel display
US5508237A (en) * 1994-03-14 1996-04-16 Corning Incorporated Flat panel display
FR2758550B1 (fr) * 1997-01-17 1999-02-12 Saint Gobain Vitrage Compositions de verre silico-sodo-calcique et leurs applications
DE19739912C1 (de) * 1997-09-11 1998-12-10 Schott Glas Alkalifreies Aluminoborosilicatglas und dessen Verwendung
US6468933B1 (en) * 1998-09-22 2002-10-22 Nippon Electric Glass Co., Ltd. Alkali-free glass and method of producing the same
DE19916296C1 (de) * 1999-04-12 2001-01-18 Schott Glas Alkalifreies Aluminoborosilicatglas und dessen Verwendung
CN103172259B (zh) * 2006-02-10 2015-10-21 康宁股份有限公司 具有高的热稳定性和化学稳定性的玻璃组合物及其制备方法
JP5233998B2 (ja) * 2007-08-31 2013-07-10 旭硝子株式会社 ガラス板およびその製造方法ならびにｔｆｔパネルの製造方法
CN103201228B (zh) * 2010-11-08 2015-11-25 日本电气硝子株式会社 无碱玻璃
KR101752033B1 (ko) * 2010-12-07 2017-06-28 아사히 가라스 가부시키가이샤 무알칼리 유리 및 무알칼리 유리의 제조 방법
JPWO2012108345A1 (ja) * 2011-02-08 2014-07-03 旭硝子株式会社 ガラス組成物およびガラス組成物を用いた太陽電池用ガラス基板、並びにディスプレイパネル用ガラス基板
US8785336B2 (en) * 2011-03-14 2014-07-22 Nippon Electric Glass Co., Ltd. Alkali-free glass
JP6191138B2 (ja) * 2012-01-12 2017-09-06 日本電気硝子株式会社 ガラス
CN108689597A (zh) * 2012-04-27 2018-10-23 Ａｇｃ株式会社 无碱玻璃及其制造方法
JP5702888B2 (ja) * 2012-04-27 2015-04-15 旭硝子株式会社 無アルカリガラスおよびその製造方法
JP6086119B2 (ja) * 2012-05-31 2017-03-01 旭硝子株式会社 無アルカリガラス基板、および、無アルカリガラス基板の薄板化方法
CN104364215A (zh) * 2012-06-05 2015-02-18 旭硝子株式会社 无碱玻璃及其制造方法
KR20200003272A (ko) * 2012-06-05 2020-01-08 에이지씨 가부시키가이샤 무알칼리 유리 및 그 제조 방법
US9505650B2 (en) * 2012-12-05 2016-11-29 Asahi Glass Company, Limited Non-alkali glass substrate
CN106396370B (zh) * 2013-04-23 2018-11-09 Agc 株式会社 无碱玻璃基板及其制造方法
WO2018025727A1 (fr) * 2016-08-05 2018-02-08 旭硝子株式会社 Substrat de verre sans alcali, substrat stratifié et procédé de production de substrat de verre
CN115557695B (zh) * 2016-08-23 2024-10-29 Ａｇｃ株式会社 无碱玻璃
JP6983377B2 (ja) * 2016-12-19 2021-12-17 日本電気硝子株式会社 ガラス

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1045422A (ja) * 1996-07-29 1998-02-17 Asahi Glass Co Ltd 無アルカリガラスおよびフラットディスプレイパネル
WO2011001920A1 (fr) * 2009-07-02 2011-01-06 旭硝子株式会社 Verre exempt d'alcali et son procédé de production

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112805255A (zh) * 2018-10-05 2021-05-14 日本电气硝子株式会社 无碱玻璃板
US12077471B2 (en) 2018-10-05 2024-09-03 Nippon Electric Glass Co., Ltd. Alkali-free glass plate
CN112823143A (zh) * 2018-10-15 2021-05-18 日本电气硝子株式会社 无碱玻璃板
CN114080369A (zh) * 2019-08-14 2022-02-22 日本电气硝子株式会社 玻璃基板
CN114080369B (zh) * 2019-08-14 2024-01-05 日本电气硝子株式会社 玻璃基板
JPWO2021261446A1 (fr) * 2020-06-25 2021-12-30
WO2021261446A1 (fr) * 2020-06-25 2021-12-30 日本電気硝子株式会社 Procédé de fabrication d'une plaque de verre à faible teneur en alcalis et plaque de verre à faible teneur en alcalis
KR20230029583A (ko) * 2020-06-25 2023-03-03 니폰 덴키 가라스 가부시키가이샤 저알칼리 유리판의 제조 방법 및 저알칼리 유리판
KR102790963B1 (ko) * 2020-06-25 2025-04-02 니폰 덴키 가라스 가부시키가이샤 저알칼리 유리판의 제조 방법 및 저알칼리 유리판
WO2024142807A1 (fr) * 2022-12-26 2024-07-04 日本電気硝子株式会社 Substrat de verre

Also Published As

Publication number Publication date
US20230146789A1 (en) 2023-05-11

Similar Documents

Publication Publication Date Title
JP7585259B2 (ja) ガラス
JP6983377B2 (ja) ガラス
WO2016185976A1 (fr) Substrat de verre non alcalin
JP7761879B2 (ja) ガラス
JP7676343B2 (ja) ガラス
US20230146789A1 (en) Glass
WO2018173833A1 (fr) Plaque de verre et procédé de fabrication associé

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17884498

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17884498

Country of ref document: EP

Kind code of ref document: A1